WO2011084993A1 - Polymères préparés à partir de mélanges de fragments monomères de réticulation n-vinylformamide multifonctionnels et n-vinylformamide réactifs hybrides et leurs utilisations - Google Patents

Polymères préparés à partir de mélanges de fragments monomères de réticulation n-vinylformamide multifonctionnels et n-vinylformamide réactifs hybrides et leurs utilisations Download PDF

Info

Publication number
WO2011084993A1
WO2011084993A1 PCT/US2011/020208 US2011020208W WO2011084993A1 WO 2011084993 A1 WO2011084993 A1 WO 2011084993A1 US 2011020208 W US2011020208 W US 2011020208W WO 2011084993 A1 WO2011084993 A1 WO 2011084993A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl
vinylformamide
functionality
reactive
moiety
Prior art date
Application number
PCT/US2011/020208
Other languages
English (en)
Inventor
Osama M. Musa
Ilya Makarovsky
Cuiyue Lei
Original Assignee
Isp Investments Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Isp Investments Inc. filed Critical Isp Investments Inc.
Priority to US13/520,810 priority Critical patent/US20130085248A1/en
Priority to US13/178,224 priority patent/US20110293540A1/en
Publication of WO2011084993A1 publication Critical patent/WO2011084993A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/08—N-Vinyl-pyrrolidine

Definitions

  • the present invention provides polymers resulting from polymerization of at least one reactive vinyl monomer moiety and a multifunctional N-vinylformamide crosslinking moiety; polymers resulting from polymerization of at least one reactive vinyl monomer moiety and a hybrid N-vinylformamide crosslinking moiety having at least one N- vinylformamide functionality and at least one other reactive vinyl functionality; polymers resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a multifunctional N-vinylformamide crosslinking moiety; and polymers resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a hybrid N-vinylformamide crosslinking moiety having at least one N- vinylformamide functionality and at least one other reactive vinyl functionality.
  • the invention further provides a wide variety of compositions
  • N-vinylamides are electron rich monomers.
  • Commonly known cyclic N-vinylamides include N-vinylpyrrolidinone (NVP) and N-vinyl-caprolactam (NVCL), and commonly known acyclic N-vinylamides are N-vinylacetamide (NVA) and N-vinylformamide (NVF).
  • Multifunctional N-vinylformamide crosslinking compounds are moieties having at least two N- vinylformamide functionalities and no other reactive functionalities.
  • Hybrid N-vinylformamide crosslinking moieties are moieties having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality that is not a N-vinylformamide functionality.
  • N-vinylamides can be accomplished through the vmylation reaction of amide through addition to acetylene, or through a trans-vinylation reaction with vinyl ether or vinyl acetate. N-vinylamides can also be prepared by cracking a vinylamide precursor.
  • the synthesis of multifunctional N-vinylamide compounds can proceed through a C-alkylation reaction using a lithium base, or tlirough the use of an N-alkylation reaction requiring the use of sodium hydride (NaH), which is typically not preferred in industrial manufacturing environments.
  • N-vinylacetamide can be de-protonated by NaOH in the presence of a phase transfer catalyst to create difunctional monomers that can be used to make polymers with cyclic backbones
  • Michael addition of N- vinyl formamides to acrylonitrile and to acrylates and methacrylates has been used for the synthesis of N-cyanoethyl-N-vinyl-formamide and 3-(N-vinylformamido)propionates, respectively.
  • the synthesis was focused on monofunctional substituted N-vinylamides.
  • the synthetic routes disclosed above relate to either multifunctional N-vinylacetamide or N-vinylpyrrolidone, or to monofunctional N- vinylformamides.
  • Crosslinking agents are bonds that link one polymer chain to another and usually result in a difference in the physical properties of the polymer.
  • Crosslinking agents contain at least two reactive groups that are reactive towards numerous groups. The extent of crosslinking and specificities of the crosslinking agents vary. The resulting modification of mechanical properties depends strongly on the crosslink density. Low crosslinking densities raise the viscosities of polymer melts. Intermediate crosslinking densities transform gummy polymers into materials that have elastomeric properties and potentially high strengths. Very high crosslinking densities can cause materials to become very rigid or glassy, such as phenol- formaldehyde materials.
  • crosslinked networks are advantageous to improve the molecular weight control, control the swelling volume, and improve the thickening property.
  • Crosslinkers are available with different spacer arm lengths. A crosslinker with a longer space arm may be used where two target groups are further apart. The availability of crosslinkers with different spacer arms allows optimization of cross-reaction efficiency. Crosslinkers with short space arms are suitable for intramolecular crosslinking.
  • the general class of lactam polymers including polyvinylpyrrolidone (PVP), are well known, as described for example in Robinson, B, V,, Sullivan, F. M., Borzelleca, J. F,, Schwartz, S.
  • PVP A Critical Review of the Kinetics and Toxicology of Polyvinylpyrrolidone (Povidone)", 1990, Lewis Publishers, InC, Chelsea, Mich.; U.S. Pat, Nos. 3,153,640, 2,927,913, 3,532,679; and Great Britain Patent no. 811,135.
  • PVP has been used extensively in medicine since 1939.
  • the toxicity of PVP has been studied extensively in a variety of species, including humans and other primates, and is extremely low.
  • Disclosures discussing crosslinkers and N-vinylformamides include WO 2009/099436, WO 2007/096400, WO 2008/032342, and United States Patent nos. 5,300,606, 5,788,950, 5,338,815, and 5,534,174.
  • the present invention provides polymers resulting from polymerization of at least one reactive vinyl monomer moiety and a multifunctional N-vinylformamide crosslinking moiety.
  • the present invention also provides polymers resulting from polymerization of at least one reactive vinyl monomer moiety and a hybrid N-vinylformamide crosslinking moiety having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality.
  • the present invention further provides polymers resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a multifunctional N- vinylformamide crosslinking moiety.
  • the present invention still further provides polymers resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a hybrid N- vinylformamide crosslinking moiety having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality.
  • the present invention further provides a wide variety of compositions comprising the above polymers.
  • the present invention provides polymers resulting from polymerization of at least one reactive vinyl monomer moiety and multifunctional N-vinylformamide crosslinking moieties or hybrid N-vinylformamide moieties, and combinations thereof.
  • the invention further provides a wide variety of compositions comprising the novel crosslinked polymers including adhesives, aerosols, agricultural compositions, beverages, cleaning compositions, coating compositions, cosmetic formulations, dental compositions, detergents, drugs, encapsulations, foods, hair sprays, lithographic solutions, membrane formulations, oilfield formulations, personal care compositions, pharmaceuticals, pigment dispersions, and the like.
  • Personal care compositions refers to such illustrative non-limiting compositions as skin, sun, oil, hair, cosmetic, and preservative compositions, including those to alter the color and appearance of the skin.
  • compositions include, but are not limited to, polymers for increased flexibility in styling, durable styling, increased humidity resistance for hair, skin, and color cosmetics, sun care water-proof/resistance, wear-resistance, and thermal protecting/enhancing compositions.
  • Dental personal care compositions include denture adhesives, toothpastes, mouth washes, and the like.
  • Pharmaceutical compositions include tablet coatings, tablet binders, transdermal patches, and the like.
  • N-vinylamides include N- vinylacetamide (NVA), N-vinyl-caprolactam (NVCL), N-vinylformamide (NVF), and N- vinylpyrrolidinone (NVP).
  • NVP N- vinylacetamide
  • NCL N-vinyl-caprolactam
  • NVF N-vinylformamide
  • NVP N- vinylpyrrolidinone
  • branched and unbranched alkyl groups refers to alkyl groups, which may be straight chained or branched. Preferably, the alkyl groups have from 1 to 6 carbon atoms. Branched groups include isopropyl, te/Y-butyl, and the like.
  • crossl inkers or crosslinker agents refers to crosslinkers or agents that contain at least two reactive groups that are reactive towards numerous groups. The extent of crosslinking and specificities of the crosslinking agents vary.
  • heteroatom refers to atoms such as oxygen, nitrogen, sulfur, and phosphorous.
  • hybrid reactive N-vinylformamide monomer moiety having one N- vinylformamide functionality and at least one other reactive non-vinyl functionality refers to moieties having one N-vinylformamide functionality and at least one other reactive functionality that is a non-vinyl functionality.
  • the at least one other reactive non-vinyl functionality in the hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality may be selected from the group consisting of epoxides, oxetanes, benzoxazines, oxazolines, and mixtures thereof.
  • Preferred illustrative examples of such moieties have the structures set out below:
  • hybrid N-vinylformamide crosslinking moiety having at least one N- vinylformamide functionality and at least one other reactive vinyl functionality refers to moieties having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality that is not a N-vinylformamide functionality.
  • moieties having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality that is not a N-vinylformamide functionality have the structures set out below:
  • K- Value is a number calculated from a dilute solution viscosity measurement of a polymer. The number is used to denote the degree of polymerization or molecular size.
  • multifunctional N-vinylformamide crosslinking moiety refers to moieties having at least two N-vinylformamide functionalities and no other reactive functionalities.
  • Illustrative examples of such moieties have the structures set out below:
  • polymer refers to a large molecule (macromolecule) composed of repeating structural units (monomers) connected by covalent chemical bonds.
  • reactive monomer moiety refers to monomer moieties reactive with multifunctional N-vinylformamide crosslinking moieties and hybrid N-vinylformamide crosslinking moieties.
  • reactive monomer moieties include anhydrides, vinyl amides, acrylates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinyl imidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinyl sulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allyl derivatives, vinyl ethers, epoxides, oxetanes, benzoxazines, oxazolines, and mixtures thereof.
  • the present invention provides polymers resulting from polymerization of at least one reactive vinyl monomer moiety and a multifunctional N-vinylformamide crosslinking moiety.
  • Preferred reactive monomer moieties may be selected from the group consisting of maleic anhydrides, vinyl amides, acrylates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinyl imidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinyl sulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allyl derivatives, vinyl ethers, and mixtures thereof.
  • Preferred multifunctional N-vinylformamide crosslinking moieties may be selected from the group consisting of:
  • More preferred multifunctional N-vinylformamide crosslinking moieties may be selected from the group consisting of:
  • the present invention further provides compositions comprising a polymer resulting from polymerization of at least one reactive vinyl monomer moiety and a multifunctional N- vinylformamide crosslinking moiety.
  • Preferred compositions are adhesive, agricultural, beverage, cleaning, coating, encapsulation, membrane, personal care, and oilfield compositions.
  • Preferred reactive monomer moieties and multifunctional N- vinyl formamide crosslinking moieties are as defined above,
  • the present invention further provides a polymer resulting from polymerization of at least one reactive vinyl monomer moiety and a hybrid N- vinyl formamide crosslinking moiety having at least one N-vinyl formamide functionality and at least one other reactive vinyl functionality.
  • Preferred reactive monomer moieties may be selected from the group consisting of maleic anhydrides, vinyl amides, acryiates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinyl imidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinyl sulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allyl derivatives, vinyl ethers, and mixtures thereof.
  • Preferred hybrid N-vinylformamide crosslinking moieties having at least one N- vinylformamide functionality and at least one other reactive vinyl functionality may be selected from the group consisting of:
  • More preferred hybrid N-vinylformamide crosslinking moieties having at least one N- vinylformamide functionality and at least one other reactive vinyl functionality may be selected from the group consisting of:
  • the present invention further provides compositions comprising a polymer resulting from polymerization of at least one reactive vinyl monomer moiety and a hybrid N- vinylformamide crosslinking moiety having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality.
  • Preferred compositions are adhesive, agricultural, beverage, cleaning, coating, encapsulation, membrane, personal care, and oilfield compositions.
  • Preferred reactive monomer moieties and hybrid N-vinylformamide crosslinking moieties having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality are as defined above.
  • the present invention further provides a polymer resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a multifunctional N- vinylformamide crosslinking moiety.
  • the at least one other reactive non-vinyl functionality in the hybrid reactive N- vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality may be selected from the group consisting of epoxides, oxetanes, benzoxazines, oxazolines, and mixtures thereof.
  • Preferred hybrid reactive N- vinylformamide monomer moieties having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality may be selected from the group consisting of:
  • a more preferred hybrid reactive N-vinylformamide monomer moiety having vinylformamide functionality and at least one other reactive non-vinyl functionality is:
  • Preferred multifunctional N-vinylformamide crosslinking moieties may be selected from the group consisting of:
  • More preferred multifunctional N-vinylformamide crosslinking moieties may be selected from the group consisting of:
  • the present invention further provides compositions comprising a polymer resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a multifunctional N-vinylformamide crosslinking moiety.
  • Preferred compositions are adhesive, agricultural, beverage, cleaning, coating, encapsulation, membrane, personal care, and oilfield compositions.
  • Preferred hybrid reactive N-vinylformamide monomer moieties having one N- vinylformamide functionality and at least one other reactive non-vinyl functionality and multifunctional N-vinylformamide crosslinking moiety are as defined above.
  • the present invention further provides a polymer resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a hybrid N- vinylformamide crosslinking moiety having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality.
  • the at least one other reactive non-vinyl functionality in the hybrid reactive N- vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality may be selected from the group consisting of epoxides, oxetanes, benzoxazines, oxazolines, and mixtures thereof.
  • Preferred hybrid reactive N- vinylformamide monomer moieties having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality may be selected from the group consisting of:
  • a more preferred hybrid reactive N-vinylformamide monomer moiety having vinylformamide functionality and at least one other reactive non-vinyl functionality is;
  • Preferred hybrid N-vinylformamide crosslinking moieties having at least one N- vinylformamide functionality and at least one other reactive vinyl functionality may be selected from the group consisting of:
  • More preferred hybrid N-vinylformamide crosslinking moieties having at least one N- vinylformamide functionality and at least one other reactive vinyl functionality may be selected from the group consisting of:
  • the present invention further provides compositions comprising a polymer resulting from polymerization of at least one hybrid reactive N-vinylformamide monomer moiety having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and a hybrid N-vinylfonnamide crosslinking moiety having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality.
  • Preferred compositions are adhesive, agricultural, beverage, cleaning, coating, encapsulation, membrane, personal care, and oilfield compositions.
  • hybrid reactive N-vinylformamide monomer moieties having one N-vinylformamide functionality and at least one other reactive non-vinyl functionality and hybrid N-vinylformamide crosslinking moieties having at least one N-vinylformamide functionality and at least one other reactive vinyl functionality are as defined above.
  • N-Allyl-N-vinylfoimamide was synthesized via a two-step reaction. The first step was the synthesis of Allyl Mesylate. Toluene (1 175 g), Allyl Alcohol (1 16.2 g, 2.0 mol) and
  • Triethylamine (253.0 g, 2.5 mol) were charged into a dry 3-L, four-neck flask fitted with a mechanical stirrer, temperature controller/thermocouple, reflux condenser, dropping funnel and nitrogen inlet. The mixture was cooled to 2-5°C, and then Methanesulfonyl Chloride (263.5 g, 2.3 mol) was added dropwise over 2 h while maintaining the temperature below 10°C. After the addition was complete, the reaction mixture was warmed to room temperature and stirred overnight. The reaction mixture became a yellow slurry. The mixture was then cooled to 2-5°C and washed with cold water. The organic layer was concentrated and dried by a rota vapor at 50- 55°C/3-4 mm Hg for 3 h to provide Allyl Mesylate, 201-214g (97.5%-98.1% pure by GC).
  • the second step was the reaction of Allyl Mesylate with N-vinylformamide to form N- Allyl-N-vinylformamide.
  • a dry 2-L, four-neck flask was fitted with a mechanical stirrer, temperature controller/thermocouple/heating mantle, reflux condenser, two dropping funnels and nitrogen inlet.
  • the apparatus was purged with nitrogen for 0.5 h and charged with /e/Y-Butyl Methyl Ether (MTBE) (774 g).
  • MTBE /e/Y-Butyl Methyl Ether
  • N-vinylformamide (59.7 g, 0.84 mol) was added dropwise into the reactor within 1 h while maintaining the temperature below 10°C. The reaction mixture was then warmed to room temperature, stirred for 1 h, and then 200 mg of tert-Butylcatechol was added. Allyl Mesylate (95.3 g, 98.9% pure, 0.7 mol) was added while the temperature was kept below 50°C, The mixture was heated to 57-58°C, refluxed for 4 h, and then cooled to room temperature. After three washes with water, the organic layer was evaporated to remove solvent by a rotavapor. The products was dried at 35-40°C/3-4 mm Hg for 3 h. The yield of the resulting product, N-Allyl-N-vinylformamide, was 68-71 g (98% pure, GC).
  • 1,8-Di-(N-vinylformamido)-3,6-dioxyoctane was synthesized via a two-step reaction.
  • the first step was the synthesis of Tri(ethylene glycol) Dimesylate.
  • a dry 3-L, four-neck flask was fitted with a mechanical stirrer, temperature controller/thermocouple, reflux condenser, dropping funnel and nitrogen inlet. The apparatus was purged with nitrogen for 0.5 h.
  • Tri(ethylene glycol) (150.2 g, 1.0 mol)
  • Triethylamine (253.0 g , 2.5 mol) were added into the flask.
  • the second step was the reaction of Tri(ethylene glycol) Dimesylate with N- vinylformamide to form l ,8-Di-(N-vinylformamide)-3,6-dioxyoctane (DVFOO).
  • l ,8-Di-(N-vinylformamide)-3,6-dioxyoctane (DVFOO) was added in a dry 2-L, four-neck flask fitted with a mechanical stirrer, temperature controller/thermocouple/heating mantle, reflux condenser, two dropping funnels and a gas inlet.
  • MTBE tert-Butyl Methyl Ether
  • the reactor was cooled to 5-8°C and Potassium tert-Butoxide 107.7 g (0.96 mol) was added with agitation.
  • N-Vinylformamide (68.2 g, 0.96 mol) was then added over a 1 h period while maintaining the temperature below 10°C. The mixture was warmed to room temperature, stirred for 1 h, and then 300 mg of tert-Butylcatechol was added. Tri(ethylene glycol) Dimesylate (TEGD) (94,5% pure, 129.6 g, 0.4 mol) was added dropwise within 15 minutes, at a rate to maintain the temperature below 55°C. The mixture was refluxed for 4 h, cooled to 2-5°C, and then vacuum filtered.
  • TEGD Tri(ethylene glycol) Dimesylate
  • 1,4-Di-(N-vinylformamido)butane was synthesized via a two-step reaction.
  • the first step was the synthesis of 1 ,4-Butanediol Dimesylate.
  • a dry 1-L, four-neck flask fitted with a mechanical stirrer, temperature control ler/thermocouple, reflux condenser, dropping funnel and nitrogen inlet was purged with nitrogen for 0.5 h.
  • 1 ,4-Butanediol 27 g, 0.3 mol
  • Triethylamine 75.9 g , 0.75 mol
  • the second step was the reaction of 1 ,4-Butanediol Dimesylate with N-vinylformamide.
  • a dry 2-L, four-neck flask was fitted with a mechanical stirrer, temperature controller/thermocouple/heating mantle, reflux condenser, dropping funnel and gas inlet.
  • the apparatus was purged with nitrogen for 0.5 h and tert-Butyl Methyl Ether (MTBE) (403 g) was then added.
  • MTBE tert-Butyl Methyl Ether
  • the reactor was cooled to 5-8°C and Potassium tert-Butoxide (67.3 g, 0.6 mol) was added with agitation.
  • N-Vinylformamide (42.7 g, 0.6 mol) was added over a 1 h period while maintaining the temperature below 10°C.
  • the second step was the reaction of 1 ,6-Hexanediol Dimesylate with N-vinylformamide.
  • a dry 2-L, four-neck flask was fitted with a mechanical stirrer, temperature controller/thermocouple/heating mantle, reflux condenser, dropping funnel and gas inlet.
  • tert-Butyl Methyl Ether (MTBE) (604 g) was charged into the reactor.
  • the reactor was cooled to 5-8°C and Potassium tert-Butoxide (121.2 g, 1.08 mol) was added with agitation.
  • N-vinylformamide (76.8 g, 1.08 mol) was added over a 1 h period while maintaining the temperature below 10°C. After the addition was complete, the mixture was slowly warmed to room temperature, stirred for 1 h, and then 300 mg of tert-Butylcatechol was added. Then 1,6-Hexanediol Dimesylate (127.1 g, 97.1 % pure, 0.45 mol) was added. The reaction mixture was slowly heated to 57-58°C and refluxed in MTBE for 2 h. After three washes with water, the organic layer was treated with silica gel in the presence of hexane. The silica gel was washed with MTBE/hexane mixture three times. The collected filtrates were then concentrated and dried by a rotavapor to provide 1 ,6-Di-(N-vinylformamido)hexane (DVFH) (90 g, 97.7% pure by GC).
  • 1,5-Di-(N-vinylformamido)-3-oxypentane was synthesized via a two-step reaction.
  • the first step was the synthesis of Di(ethylene glycol) Dimesylate.
  • a dry 3-L, four-neck flask was fitted with a mechanical stirrer, thermocouple/temperature controller, reflux condenser, dropping funnel and nitrogen inlet. The apparatus was purged with nitrogen for 0.5 h.
  • MTBE (1460 g) Di(ethylene glycol) (106.1 g, 1.0 mol) and Trlethylamine (253.0 g, 2.5 mol) were added to the flask.
  • the second step was the reaction of Di(ethylene glycol) Dimesylate with N- vinylformamide to form 1,5-Di-(N-vinylformamido)-3-oxypentane (DVFOP).
  • a dry 3-L, four- neck flask was fitted with a mechanical stirrer, thermocouple/temperature controller/heating mantle, reflux condenser, dropping funnel and nitrogen inlet.
  • the apparatus was purged with nitrogen for 0.5 h and MTBE (942 g) was added.
  • the reactor was cooled to 5-8°C and Potassium tert-Butoxide 188.5 g (1.68 mol) was added with agitation.
  • N-vinylformamide (1 19.5 g, 1.68 mol) was then added dropwise over a 1 h period while maintaining the temperature below 10°C. The mixture was slowly warmed to room temperature, stirred for 1 h, and then 400 mg of tert-Butylcatechol was added. Di(ethylene glycol) Dimesylate (DEGD) (192.3g, 95.5% pure, 0.7 mol) was then added within 0.5 h. The mixture was heated to 57-58°C, refluxed for 3 h, cooled to 2-5°C, and then filtrated. The precipitate was washed witli MTBE. The filtrate was washed with water and treated with silica gel.
  • DEGD Di(ethylene glycol) Dimesylate
  • l ,l l-Di-(N-vinylformamido)-3,6,9-trioxyundecane was synthesized via a two-step reaction.
  • the first step was the synthesis of Tetra (ethylene glycol) Dimesylate.
  • a dry 3-L, four- neck flask was fitted with a mechanical stirrer, thermocouple/temperature controller, reflux condenser, dropping funnel and nitrogen inlet. The apparatus was purged with nitrogen for 0.5 h.
  • Tetra(ethylene glycol) (155.4 g, 0.8 mol)
  • Triethylamine (202.4 g, 2.0 mol
  • the mixture was cooled to 2-5°C and Methanesulfonyl Chloride (210.8 g, 1.84 mol) was added within 2 h while maintaining the temperature below 10°C.
  • the reaction mixture was then warmed to room temperature and stirred overnight, After two washes with cold water, the organic layer was evaporated to dryness by a rotavapor to provide Tetra(ethylene glycol) Dimesylate with a yield of 268 g and a purity of 81.1% (GC analysis).
  • the second step was the reaction of Tetra(ethylene glycol) Dimesylate with N- vinylformamide to form 1,1 l-Di-(N-vinyIformamido)-3,6,9-trioxynndecane (DVFTU).
  • a dry 2- L, four-neck flask was fitted with a mechanical stirrer, temperature controller/ thermocouple/heating mantle, reflux condenser, dropping funnel and nitrogen inlet.
  • the apparatus was purged with nitrogen for 0.5 h and MTBE (506 g) was added.
  • the reactor was cooled down to 5-8°C and then Potassium tert-Butoxide 87.5 g (0.78 mol) was added with agitation.
  • N-vinylformamide (55.4 g, 0.78 mol) was added within 1 h while maintaining the temperature below 10°C.
  • the mixture was warmed to room temperature, stirred for 1 h, and then 250 mg of tert-Butylcatechol was added.
  • Tetra(ethylene glycol) Dimesylate (129.6g, 81.1% pure, 0.3 mol) was added within 0.5 h. The mixture was heated to 60-62°C, refluxed for 4 h, cooled to 2-5°C, and then filtrated. The precipitate was washed with cold MTBE. The collected filtrate was treated with silica gel in the presence of hexane. The filtrate was concentrated and dried by a rotavapor to provide 1,1 l-Di-(N-vinylformamido)-3,6 ⁇ 9- trioxyundecane (DVFTU) (73 g , 97.0% pure by GC).
  • DVDTU 1,1 l-Di-(N-vinylformamido)-3,6 ⁇ 9- trioxyundecane
  • a dry 1 -L, four-neck flask was fitted with mechanical stirrer, temperature controller/thermocoxiple/heating mantel, reflux condenser, dropping funnel and nitrogen inlet.
  • the apparatus was purged with nitrogen for 0.5 h and charged with Toluene (387 g).
  • the flask was cooled to 10-15°C and 64.5 g of Potassium tert-Butoxide (0.575 mol) was added.
  • N- vinylformamide (40.9 g, 0.575 mol) was then added within 0.5 h while maintaining the temperature below 25 °C. When the addition was complete, the mixture was stirred for 1 h.
  • Tert-Butylcatechol 140 mg was added and stirring was continued for 1 h.
  • Heptane 1000 g was charged into a 2-liter four-necked glass kettle equipped with feeding pumps, anchor agitator, thermocouple and condenser. After nitrogen purge, the reactor was heated to 62°C.
  • a Feed I was prepared by mixing 100 g N-vinylpyrrolidone and 2.0 g 1,8- Di-(N-vinylformamido)-3,6-dioxyoctane.
  • a Feed II was prepared by weighing 100 g of Acrylic Acid (AA) into a bottle.
  • the Heptane was held at 62°C for 0.5 h and then 0.344 g Trigonox 25 C75 and 1.0 g Di-tert-Butyl Peroxide (DTBP) were added into the kettle. Simultaneously, Feeds I and II were metered into the reactor over 4 h. After the feeding was complete, the reaction was held at 62°C for 1 h, and then increased to 90°C within 30 m in. A quantity of 0.158 g of Trigonox 25C75 was added every hour for a total of two times. After the last charge of Trigonox 25C75, the reaction was held for 1 h.
  • DTBP Di-tert-Butyl Peroxide
  • the reaction mixture was cooled to 40°C, transferred to a 2-L high pressure reactor, and then charged with 1.0 g of Di-tert-Butyl Peroxide. After three purges with nitrogen, the reactor was heated to 120°C. The reaction was held for 10 h and then cooled to room temperature. Solvent was removed and the residual was dried in a vacuum oven to provide a white powder. Gas cliromatography analysis showed that the residual N- vinylpyrrolidone was 0.13%. The polymer contains 62% crosslinked PVP.
  • Heptane 1000 g was charged into a 2-liter four-necked glass kettle equipped with feeding pumps, anchor agitator, thermocouple and condenser. After a nitrogen purge, the reactor was heated to 62°C.
  • a Feed I was prepared by mixing 100 g of N-vinylpyrrolidone and 2.0 g of 1,5-Di-(N-vinylformamido)-3-oxypentane.
  • a Feed II was prepared by weighing 100 g of Acrylic Acid (AA) into a bottle. The Heptane was held at 62°C for 30 min, then 0.344 g of Trigonox 25 C75 and 1 .0 g of Di-tert-Butyl Peroxide was added into the kettle.
  • Feeds I and II were metered into the reactor over 4h. After the feeding was complete, the reaction was held at 62°C for 1 h and then increased to 90°C within 30 min. A quantity of 0.158 g of Trigonox 25C75 was added every hour for a total of 2 times. After the last charge of Trigonox 25C75, the reaction was held for 1 h. The reaction mixture was cooled to 40°C, transferred to a 2-L high pressure reactor then charged with 1.0 g of Di-tert-Butyl Peroxide. After three purges with nitrogen, the reactor was heated to 120°C and held for 10 hours. The r reaction mixture was then cooled to room temperature. Solvent was removed and the residual was dried in a vacuum oven to provide a white powder. Gas chromatography analysis showed that the residual N-vinylpyrrolidone was 0.078%. The polymer contains 41-48% crosslinked PVP.
  • Heptane 1000 g was charged into a 2-liter four-necked glass kettle equipped with feeding pumps, anchor agitator, thermocouple and condenser. After a nitrogen purge, the reactor was heated to 62°C A Feed I was prepared by mixing 100 g of N-vinylpyrrolidone and 2.0g of 1,8-Di-(N-vinylformamido)hexane. A Feed II was prepared by weighing 100 g of Acrylic Acid (AA) into a bottle. The Heptane was held at 62°C for 30 min, then 0.344 g Trigonox 25 C75 and 1.0 g Di-tert-Butyl Peroxide were added into the kettle.
  • AA Acrylic Acid
  • Feeds I and II were metered into the reactor over 4 h. After the feeding was complete, the reaction was held at 62°C for 1 h and then increased to 90°C within 30 min. A quantity of 0.158 g of Trigonox 25C75 was added every hour for a total of 2 times. After the last charge of Trigonox 25C75, the reaction was held for 1 h. The reaction mixture was cooled to 40°C, transferred to a 2-L high pressure reactor, and then charged with 1.0 g of d-t-butyl peroxide. After three purges with nitrogen, the reactor was heated to 120°C, held for 10 h, and then cooled to room temperature. Solvent was removed and the residual was dried in a vacuum oven to provide a white powder. Gas chromatography analysis showed that the residual VP was ⁇ 0.19%. The polymer contains 60-70% crosslinked PVP.
  • Heptane 1000 g was charged into a 2-liter four-necked glass kettle equipped with feeding pumps, anchor agitator, thermocouple and condenser. After a nitrogen purge, the reactor was heated to 62°C A Feed I was prepared by mixing 100 g of N-vinylpyrrolidone and 2.0g of 1,4-Di-(N-vinylformamido)butane. A Feed II was prepared by weighing 100 g of Acrylic Acid (AA) into a bottle. The reaction was held at 62°C for 30 min then 0.344 g Trigonox 25 C75 and 1 .0 g Di-tert-Butyl Peroxide were added into the kettle.
  • AA Acrylic Acid
  • Feeds I and II were metered into the reactor over 4 h. After the feeding was complete, the reaction was held at 62°C for 1 h then increased to 90°C. A quantity of 0.158 g of Trigonox 25C75 was added every hour for a total of 2 times. The reaction was held for 1 h, cooled to 40°C, and then transferred to a 2-L high pressure reactor. A quantity of 1.0 g of d-t-butyl peroxide was added into the reactor. After three purges with nitrogen, the reactor was heated to 120°C, held for 10 h, and then cooled to room temperature. Solvent was removed and the residual was dried in a vacuum oven to provide a white powder. Gas chromatography analysis showed that the residual N-vinylpyrrolidone was ⁇ 0.1%. The polymer contains 60-70% crosslinked PVP.
  • Heptane 1000 g was charged into a 2-L four-neck resin kettle equipped with an anchor stirrer, thermocouple, one feeding tube, reflux condenser and gas inlet. After a nitrogen purge with agitation, the reactor was heated to 65°C and held for 30 min. Then 520 ⁇ Trigonox 25 C75 was charged and a premix of 0.90 g of l ,5-Di-(N-vinylformamido)-3-oxypentane and 200 g of N-vinylpyrrolidone was fed in over 6 h. The reaction was held at 65°C for 1 h and 200 ⁇ of Trigonox 25 C75 was charged.
  • Heptane (1000 g) was charged into a 2-L four-neck resin kettle equipped with an anchor stirrer, thermocouple, one feeding tube, reflux condenser and gas inlet. After a nitrogen purge and agitation, the reactor was heated to 65°C and held for 30 min. Then 520 ⁇ Trigonox 25 C75 was charged and a premix of 0.90 g 1,8-Di-(N-vinylformamido)-3,6-dioxyoctane and 200 g N-vinylpyrrolidone was fed in over 6 h. The reaction was held at 65°C for 1 h and 200 ⁇ Trigonox 25 C75 was charged.
  • reaction mixture After 1 h of reaction, the reaction mixture was cooled, transferred into a 2-L high pressure reactor then 1.0 g Luperox 101 was charged. The reaction mixture was heated to 130°C, stirred for 10 h then cooled to room temperature and dried to provide a white powder. GC analysis showed the residual N-vinylpyrrolidone was less than lOOppm. The polymer contains 55-70% crosslinked PVP.
  • Heptane 1000 g was charged into a 2-L four-neck resin kettle equipped with an anchor stirrer, thermocouple, one feeding tube, reflux condenser and gas inlet. After a nitrogen purge and agitation, the reactor was heated to 65°C and held for 30 min. Then 520 ⁇ 1 Trigonox 25 C75 was charged and a premix of 0.90 g of 1,4-Di-(N-vinylformamido)butane and 200 g of N- vinylpyrrolidone was fed in over 6 h. The reaction was held at 65°C for 1 h and 200 ⁇ Trigonox 25 C75 was charged.
  • reaction mixture After 1 h of reaction, the reaction mixture was cooled, transferred into a 2-L high pressure reactor, then 1.0 g Luperox 101 was charged. The reaction mixture was heated to 130°C, stirred for 10 h then cooled to room temperature and dried to provide a white powder. GC analysis showed the residual N-vinylpyrrolidone was less than lOOppm. The polymer contains 55-70% crosslinked PVP.
  • Example 16 Heptane (1000 g) was charged into a 2-L four-neck resin kettle equipped with an anchor stirrer, thermocouple, one feeding tube, reflux condenser and gas inlet. After a nitrogen purge and agitation, the reactor was heated to 65°C and held for 30 min. Then 520 ⁇ 1 Trigonox 25 C75 was charged and a premix of 0.90 g of 1,6-Di-(N-vinylformamido)hexane and 200 g of N- vinylpyrrolidone was fed in over 6 h. The reaction was held at 65°C for 1 h and 200 ⁇ Trigonox 25 C75 was charged.
  • reaction mixture was cooled, transferred into a 2-L high pressure reactor, then 1.0 g Luperox 101 was charged.
  • the reaction mixture was heated to 130°C, stirred for lOh then cooled to room temperature and dried to provide a white powder.
  • GC analysis showed the residual N-vinylpyrrolidone was less than lOOppm.
  • the polymer contains 55-70% crosslinked PVP.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)

Abstract

La présente invention a pour objet des polymères résultant de la polymérisation d'au moins un fragment monomère vinylique réactif et d'un fragment de réticulation N-vinylformamide multifonctionnel ; des polymères résultant de la polymérisation d'au moins un fragment monomère vinylique réactif et d'un fragment de réticulation N-vinylformamide hybride ayant au moins une fonctionnalité N-vinylformamide et au moins une autre fonctionnalité vinylique réactive ; des polymères résultant de la polymérisation d'au moins un fragment monomère N-vinylformamide réactif hybride ayant une fonctionnalité N-vinylformamide et au moins une autre fonctionnalité non vinylique réactive et d'un fragment de réticulation N-vinylformamide multifonctionnel ; et des polymères résultant de la polymérisation d'au moins un fragment monomère N-vinylformamide réactif hybride ayant une fonctionnalité N-vinylformamide et au moins une autre fonctionnalité non vinylique réactive et d'un fragment de réticulation N-vinylformamide hybride ayant au moins une fonctionnalité N-vinylformamide et au moins une autre fonctionnalité vinylique réactive. L'invention concerne en outre une large variété de compositions comprenant les nouveaux polymères réticulés.
PCT/US2011/020208 2010-01-07 2011-01-05 Polymères préparés à partir de mélanges de fragments monomères de réticulation n-vinylformamide multifonctionnels et n-vinylformamide réactifs hybrides et leurs utilisations WO2011084993A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/520,810 US20130085248A1 (en) 2010-01-07 2011-01-05 Polymers prepared from mixtures of multifunctional n-vinylformamide and hybrid reactive n-vinylformamide crosslinking monomer moieties and uses thereof
US13/178,224 US20110293540A1 (en) 2010-01-07 2011-07-07 Branched polymers, compositions, and uses thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29289710P 2010-01-07 2010-01-07
US61/292,897 2010-01-07

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/178,224 Continuation-In-Part US20110293540A1 (en) 2010-01-07 2011-07-07 Branched polymers, compositions, and uses thereof

Publications (1)

Publication Number Publication Date
WO2011084993A1 true WO2011084993A1 (fr) 2011-07-14

Family

ID=44225080

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/020208 WO2011084993A1 (fr) 2010-01-07 2011-01-05 Polymères préparés à partir de mélanges de fragments monomères de réticulation n-vinylformamide multifonctionnels et n-vinylformamide réactifs hybrides et leurs utilisations

Country Status (2)

Country Link
US (3) US20110166308A1 (fr)
WO (1) WO2011084993A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10202341B2 (en) 2010-01-11 2019-02-12 Isp Investments Llc Compositions comprising a reactive monomer and with a urea or urethane functional group
WO2011085077A1 (fr) * 2010-01-11 2011-07-14 Isp Investments Inc. Monomère réactif pour un revêtement et/ou un revêtement réactif
US20130004667A1 (en) * 2010-01-11 2013-01-03 Isp Investments Inc. Compositions comprising a reactive monomer and with a urea or urethane functional group
EP2646539B1 (fr) 2010-12-01 2019-04-03 ISP Investments LLC Compositions de coiffage durables et leurs utilisations
DE102011088926A1 (de) * 2011-12-19 2013-06-20 Beiersdorf Ag Haarstylingformulierung zur Erstellung eines flexiblen Haltes durch Einsatz von Octanohydroxamsäure
DE102011088957A1 (de) * 2011-12-19 2013-06-20 Beiersdorf Ag Wirkstoffkombinationen aus Pirocton Olamin und einer oder mehreren physiologischunbedenklichen Hydroxamsäure sowie kosmetische oder dermatologischeZubereitungen, solche Wirkstoffkombinationen enthaltend
US20130333888A1 (en) * 2012-06-19 2013-12-19 Marco Tulio Rincon-Torres Self-degrading ionically cross-linked biopolymer composition for well treatment
WO2014106516A1 (fr) * 2013-01-03 2014-07-10 Tripp Gmbh & Co. Kg Préparation adhésive pour prothèses de la mâchoire
US9353269B2 (en) 2013-03-15 2016-05-31 American Sterilizer Company Reactive surface coating having chemical decontamination and biocidal properties
US9672952B2 (en) 2013-08-14 2017-06-06 Industrial Technology Research Institute Polymer and conductive composition
EP3377549A4 (fr) * 2015-11-20 2019-07-03 ISP Investments LLC Polymères prolifères comprenant des fractions lactamiques
US10227495B2 (en) * 2016-07-29 2019-03-12 Georgia Southern Research and Service Foundation Biocidal biopolymer coatings
MX2019014395A (es) 2017-06-02 2020-02-10 Carbonet Nanotechnologies Inc Agentes secuestrantes, kits de los mismos, y metodos para usar agentes secuestrantes y kits de los mismos.
CN115884747A (zh) * 2020-08-06 2023-03-31 高露洁-棕榄公司 包含特定防腐剂体系的口腔护理组合物
US20240099451A1 (en) * 2022-09-28 2024-03-28 Zest Ip Holdings, Llc Dental composition and related device and method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774285A (en) * 1985-09-26 1988-09-27 Basf Aktiengesellschaft Preparation of water-soluble copolymers containing vinylamine units, and their use as wet strength agents and dry strength agents for paper
US5534174A (en) * 1990-04-20 1996-07-09 Ethyl Petroleum Additives, Inc. Graft copolymer comprising a star-shaped polymer and an n-allyl amide
US5569725A (en) * 1994-10-14 1996-10-29 Air Products And Chemicals, Inc. N-vinyl-n-acyl urea resins
US7135598B2 (en) * 2002-09-06 2006-11-14 University Of Pittsburgh N-vinylformamide derivatives, polymers formed therefrom and synthesis thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0473881B1 (fr) * 1990-09-03 2001-11-07 Showa Denko Kabushiki Kaisha Agent d'absorption de liquide
US5788950A (en) * 1994-08-03 1998-08-04 Showa Denko K.K. Method for the synthesis of mixed metal oxide powders
WO2010144588A1 (fr) * 2009-06-10 2010-12-16 Conocophillips Company-Ip Services Group Polymère pouvant gonfler, comportant des sites anioniques
GB2483381B (en) * 2009-06-15 2013-09-04 Conocophillips Co Swellable polymer with cationic sites

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4774285A (en) * 1985-09-26 1988-09-27 Basf Aktiengesellschaft Preparation of water-soluble copolymers containing vinylamine units, and their use as wet strength agents and dry strength agents for paper
US5534174A (en) * 1990-04-20 1996-07-09 Ethyl Petroleum Additives, Inc. Graft copolymer comprising a star-shaped polymer and an n-allyl amide
US5569725A (en) * 1994-10-14 1996-10-29 Air Products And Chemicals, Inc. N-vinyl-n-acyl urea resins
US7135598B2 (en) * 2002-09-06 2006-11-14 University Of Pittsburgh N-vinylformamide derivatives, polymers formed therefrom and synthesis thereof

Also Published As

Publication number Publication date
US20130085248A1 (en) 2013-04-04
US20110166308A1 (en) 2011-07-07
US20110293540A1 (en) 2011-12-01

Similar Documents

Publication Publication Date Title
WO2011084993A1 (fr) Polymères préparés à partir de mélanges de fragments monomères de réticulation n-vinylformamide multifonctionnels et n-vinylformamide réactifs hybrides et leurs utilisations
KR101848781B1 (ko) 폴리스티렌-폴리올레핀-폴리스티렌 삼중블록 공중합체 및 이의 제조 방법
WO2009023843A1 (fr) Polymères de polyvinylamide contenant des fonctionnalités polymérisables
JP7101738B2 (ja) ポリオレフィン－ポリスチレン系多重ブロック共重合体、それを製造するための有機亜鉛化合物及びポリオレフィン－ポリスチレン系多重ブロック共重合体の製造方法
US11066502B2 (en) Maleate-based copolymers and methods for preparing the same
JPS63137903A (ja) 連鎖端で機能化された重合体及びその製法
JP2010510348A (ja) 官能性炭化水素ポリマーおよびその生成法
WO2018212945A1 (fr) Copolymères de méthacrylate d'hydroxyéthylpyrrolidone/méthacrylate de glycidyle
CN101528782A (zh) 酸官能化的梯度嵌段共聚物
CN105980419B (zh) 经选择的聚衣康酸聚合物的可溶水性组合物
CN107880263A (zh) 一种侧链含寡聚乙二醇的温度响应性聚类肽及其制备方法
US5321110A (en) Cationic polymer compositions
CA2161576A1 (fr) Copolymeres solubles pour cosmetiques capillaires
WO2019230543A1 (fr) Polymère ayant une structure de dipicolylamine, son procédé de production, agent antimicrobien et procédé antibactérien
US20220204747A1 (en) Polyolefin-Polystyrene Multi-Block Copolymer and Method for Producing Same
KR20090092015A (ko) ｐＨ 응답성 폴리에틸렌 옥사이드계 공중합체 및 그 제조방법
White et al. Synthesis of 3-alkylated-1-vinyl-2-pyrrolidones and preliminary kinetic studies of their photopolymerizations
Pinschmidt Jr et al. Amine functional polymers based on N-ethenylformamide
CN113929809B (zh) 一种季铵盐类聚合物及其制备方法
US4517329A (en) Polymeric antitumor agent
CN1831022A (zh) 一种pH响应的含氟嵌段共聚物及其制备方法
US6624270B1 (en) Copolymers derived from vinyl dicyanoimidazoles and other monomers
WO1993022380A1 (fr) Polymeres de pyrrolidone vinylique et acrylamides aminoalkyles
JP2007532734A (ja) Ｋ値≧１２０を有するポリビニルラクタムの水中水型分散液を製造するための方法
JP2908555B2 (ja) カチオン性ゲル基材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11732078

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 13520810

Country of ref document: US

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205N DATED 15.10.2012.)

122 Ep: pct application non-entry in european phase

Ref document number: 11732078

Country of ref document: EP

Kind code of ref document: A1